SYNTHESES AND REACTIONS OF ACYCLIC N,N-DIACYLGLYCINES
SYNTHESES AND REACTIONS OF ACYCLIC N,N-DIACYLGLYCINES
复制标题
DOI：
10.1021/ja01138a030
复制
发表时间：
1952-01-01
影响因子：
15
通讯作者：
COREY, EJ
中科院分区：
文献类型：
--
作者：
SHEEHAN, JC;COREY, EJ
合成了三种可能的青霉素类化合物的中间体-二酰甘氨酸。每种情况下的酸都是通过相应的苄基酯的氢解得到的。苄酯的合成通过三条不同的路线完成：(1)N-单甘氨酸苄酯的酰化，(2)二胺与卤乙酸苄酯的烷基化和(3)O-酰基异酰胺的形成和重排。与环状N，N-二酰基氨基酸氯化物形成鲜明对比的是，非环状N，N-二酰甘氨酸-1氯化物足够稳定，仅当酰基为芳酰基时才容易分离。最近报道了一种新的方法来制备稠合/3-内酰胺-噻唑烷类化合物，该方法涉及受保护的氨基酸氯化物(如丁二酰氯)和噻唑啉的相互作用。将反应延伸到N，N-二酰基甘氨酰氯，然后选择性地对一个酰基进行水解，将得到具有天然青霉素所特有的6-酰氨基取代基的β-内酰胺-噻唑烷。选择性水解似乎是可行的，因为在温和的条件下，在碱的存在下，二胺能迅速水解成酰胺。3我们现在正在报道三种无环二酰甘氨酸的制备和相应的酸性氯化物N，N-二乙酰甘氨酸的合成研究
Three acyclic,-diacylglycines have been prepared which represent possible intermediates in the synthesis ofpenicillinlike compounds. The acids were obtained in each case by hydrogenolysis of the corresponding benzyl esters. Synthesis of the benzyl esters was accomplished by three different routes:(1) acylation of an N-monoacylglycine benzyl ester,(2) alkylation of a diamide with a benzyl haloacetate and (3) formation and rearrangement of an O-acylisoamide. In sharp contrast to cyclic NN-diacylamino acid chlorides, the acyclic N, N-diacylglycy 1 chlorides were found to be sufficiently stable to permit easy isolation in pure form only when the acyl groups were aroyl.Recently a new method has been reported2 for the preparation of fused/3-lactam-thiazolidines involving interaction of protected aminoacid chloride derivatives (such as succinylglycyl chloride) and thiazolines. Extension of the reaction to acy-clic N, N-diacylglycyl chlorides and subsequent selective hydrolysis of one acyl group would lead to ß-lactam-thiazolidines possessing the 6-acylamino substituent characteristic of the natural penicillins. A selective hydrolysis appears feasible since diamides are hydrolyzed rapidly to amides under mild conditions in the presence of base. 3 We are now reporting the preparation4 of three acyclic diacylglycines and studies on the synthesis of the corresponding acid chlorides, N, N-diacetylglycy 1